Sulfur dyes and their manufacture.



. a citizen oi tlie German HEINRICH HEIVIA'CIN, GF DESSAU, GEBMNY,ASSIGNOE TO ACTEN GESELLSCHAFT .FLINJXNT;LRETXGH, 0F EERLIN, GEEME'Y.

SLFE EYES AND THEIR MANUFACTUR.

En Brewing,

To all whom t may Conua/w:

Re it known that l, HEINRICH HEIMANN, Empire, residing at Dessau,Germany, luy Q. address' being Friedricli-Sclineiderstrasse 63, Bessau,Gen many, have invented certain new and useful 'improvements in SulfurDyes and Their Manufacture, of which the following is a speciiica'tion.l

it bas been round that new value-bie sulfur-ized dyes can be obtained bythe aotion of sulfur upon a mixture oi an amino, di-

compound with a. C-alkylatecl diamin of tbe benzeneand naphtbaleneseries. Thus for instance acc-ordino; to niy invention a mixture ofnieta-toluyilenediarnin or para-toluylenediamin or Xylylenediamin, etc.,or of a N-aryl-dcrivative of tliese diamine, such as for instance anaptiiybnieta-toluyleuedianiin or the corresponding, or olea nitrcaminwith amino-azo-benzene, benzene-ano-beta-napli tbylainin, orbenzene-azo-alplianaphtliyl amin, etc., may be acted upon with sulfur.Furthermore mixtures of inetatol-uyienediamin with a beuzeneazo--phenolor with a benzene-azo-naphtliol maybe brought into reaction with sul-iuraccording to my invention.

The new sulfur dyes Sess a beautiful shade and are very fast to washingand against boiling diluted acids. The tints obtained witb. these newdyes are numerous; they vary, generally speaking, from beautiful olivesto beautitui reddish browns or black browns or brownisli orange.

The following examples serve to iilustrate the invention, the rartsbeing by weig At:

(1.,) 12 parts of meta-toluylenedianiin, 2O parts of aniino-azo-benzeneand 8G parts of sulfur are heated toffetlier dui-ino about 4' b c hoursupon say ISO-230 C. andtben during," about l to 2 hours to say 236-2699The melt thus obtained is rendered soluble in the usual way by treatingit with a concentrated solution of sodium sulid. The new dye may beseparated as usually for instance by i troclucing a current of air; itproduceson uninordanterl cotton in a dyebatn con 'ning an alkali metalsuliri beautiful olive shades which are fast to washing and to boilingdiluted acids.

(2.) A. mixture of l() parts of metatoluylenediamin, 2O parts ofbenzene-azo-betanaphthylamin and of part-s of sulfur is Specicaton ofLetters atent.

ippllcation flied January 31, 2915.

raeeneea nee. es, er e. Serial No. 3,805.

heated during about Qfhours to say 180 to 220 C. and then during say 4-8hours for instance to 220-2600 C. The new dye may be rendered solubleand separated as indicated in example (l) g it dyes unrnordanted cottona. beautiful reddish brown. fast to washing and diluted boiling acid.

ln a similar manner from a mixture of Ineta-toluylene-diamin andbenzene-azonlpha-naplitbylamin a beautiful brown dye is obtained theflyeings of which are fast to washing and to boiling dilute acids. The

new dye in the dry state when pulverized forms a dark brown powder,which is inso1- -uble or nearly insoluble in the usual organic solventsand diliicultly soluble in concentrated sulfuric acid to a black brownsolution which is decolorized on the addition of aluminium powder.

lt is obvious that the present invention is for 'instance9ara-nitrobenzeneazobresol,`

tlie hydroxyrizo-compound may be used which is obtained by combiningpara-nitrodiazobenzene with a crude cresol containing the orthoas wellas the metaand para cresol. The tinte thus obtained, generally speaking,are very similar.

Having now described my invention what l claim -is,h

l. lYew sulfurizecl dyes, which can be ob` tained bythe action of sulfurupon a mixture or" an amino derivative of the benzene-azonaphthaleneseries with a C-alkylated diamin of the aromatic series, the tints ofwhich vary from beautiful olives to beautiful browns, the shadesobtained on unrnordanted cotton with the aid of tbe new dyes being,generally speaking, very fast to washing und to diluted boiling acids,and these new dyes being insoluble or nearly insoluble in the usualorganic solvents and dilicultly soluble in concentrated sulfuric acid,but

easily soluble in an aqueous solution of an alkali metal sulfid and inan alkaline solution of a hydrosulite.

2. New sulfur-ized dyes, which con be obtained by the action of sulfurupon a mixture of a benzene-azo-naphtliylamin with u C- alkylateddianiin of the benzene series tlie tints of Which vary from beautifulolives to beautiful browns7 the shades obtained en unmordanted cottonwith the aid of the new dyes being, generally speaking, very fast towashing und to diluted boiling acids, these new dyes being,` insolubleor nearly insoluble in the usual organic solvents :incl diflicultlysoluble in concentrated surfuric acid, but easily soluble in an aqueoussolution of an alkali metal sulficl and in an allmline Solution of ahycliosulite.

3. A new sulurized dye, which can be obtained by the action of sulfurupon a mixture of benzene-:1z0-alpha napththylamin withInetwtoluylenediamin, which new (lye 'in the dry state and pulverizedforms a dark brown powder, insoluble or nearly insoluble 1n the usualorganic solvents and f liiiicuitly soluble 1n concentrated sulfuricacid. to a tive of tbe ,sultui upon s 1n ,black brown solution, which isdeoolorizefl on the addition of aluminium powder, this new dye beingreadily soluble in an aqueous solution of in alkali metal sulfifl and inan alkaline hydrosul'ite solution, and which new i'lye produces onunxnordsnte cotton from u .dye-beth containing an alkali metal sulid :ibeautiful bro-Wn tint fest to Washing und to boilingdiluted acids.

4f. ,il'ie liereinbeforedescribed manufacture of new suluriZe-fl dyes byacting with sulfur upon o niixtue ci an amino-deriva-.'.aphtlialene-seies .5. The

bereinbefo -deseribed manufacture of new sulfuri i dyes by acting with uof e, benzene-szonapliibylsniin with nieta,-toliiylenedismin lintestimony' wliei'eolf l bave hereunto set my hand in presence ci" twosubscribing Witnesses.

HENRCH HEMNN. lVitiiesse ARTHUR Ronny, L, QnrmMANN,

